Gravimetry – any method in which the signal is a 4.

Of known composition after it is dried or

mass or a change in mass
THREE PROCESS:
1. Precipitation – analyte is converted to solid,
insoluble
2. Isolation – freeing from impurities
3. Weighing
GRAVIMETRIC METHODS OF ANALYSIS
- are based on the measurement of mass
- is the quantitative determination of analyte
concentration through a process of
precipitation of the analyte, isolation of the
precipitate, and weighing the isolated product.
TWO MAJOR TYPES OF GRAVIMETRIC
METHODS:
• Precipitation Methods
- Analyte is converted into sparingly soluble
precipitate
- Precipitate is then filtered, washed free of
impurities, and converted to a product of
known composition by suitable heat
treatment, and the product is weighed
• Volatilization Methods
-The analyte or its decomposition products
are volatilized at a suitable temperature
-The volatile product is then collected and
weighed
ignited
Steps in analyzing using GRAVIMETRIC
method:
1. Prepare the analyte solution
 Select the precipitating reagent (specific if
possible)
 Adjustments to maximize precipitation
2. Precipitation of analyte
 Large crystals
 Solubility:
o high – some of the analyte is left in
the solution
o low – greater tendency to form in
solid
(Q−S)
 Von Weinarn Ratio:  relative
S
supersaturation
Impurities in Precipitation
Coprecipitation – unwanted species along with the
analyte of interest
 Surface absorption – unwanted material at
the surface of the precipitate
 Inclusion – contaminant ion that replaces an
ion in the lattice of a crystal
 Occlusion – coprecipitated impurity trapped
within a precipitate as it forms
INCREASING THE IMPURITY

USES OF GRAVIMETRIC 1. Digestion

2. Filtration
• For chemical analysis of ores and industrial 3. Washing
materilas 4. Drying or Igniting
• Calibration of instrumentation
• Element analysis of inorganic compounds What Factors Determine Particle Size?
CRITERIA FOR GRAVIMETRIC ANALYSIS Particle size is influenced by precipitate solubility,
temperature, reactant concentrations, and the rate at
1. The desired substance must completely
which reactants are mixed
precipitate from solution
2. The weighed form of the product should be TECHNICAL APPLICATIONS OF
of known composition. GRAVIMETRIC METHODS
3. The product should be "pure" and easily
filtered. 1. Inorganic Precipitating Agents

CHARACTERISTICS OF IDEAL 2. Reducing Agents

PRECIPITATING REAGENTS: 3. Organic Precipitating Agents
1. Readily filtered and washed free of 4. Organic Functional Group Analysis
contaminants
2. Of sufficiently low solubility so that no 5. Volatilization Methods
significant loss of the solid occurs during
filtration and washing
3. Unreactive with constituents in the
atmosphere
VOLUMETRIC METHOD OF ANALYSIS
Volumetric Analysis
 involves the measurement of volume of a
solution of known concentration which is
used to determine the concentration of the
analyte
 any method of quantitative chemical analysis
in which the amount of a substance is
determined by measuring the volume that it
occupies or the volume of a second substance
that combines with the first known
proportions more correctly called titrimetric
analysis
Jean-Baptiste-Andre Dumas – French Chemist,
devised the procedure for determining the proportion
of nitrogen combined with other elements in organic
compounds.
Titration – quick, accurate and widely used way of
measuring the amount of a substance in a solution
Titrants – standard solution with known
concentration needed to react with an unknown
quantity of a second substance
Stoichiometric Reaction – reaction with definite
whole number ration between a and b
End point – abrupt change in some physical and
chemical property of the sample solution ; the point
at which some detection technique tells you that
chemical equivalence has been reached. The end point
may occur before or after the equivalence point,
giving a titration error.
Equivalence point – the point at which just
sufficient reagents is added for complete reaction with
the sample ; point of stoichiometric chemical
equivalence
FEATURES OF TITRATION
 The reaction has to be complete
 The reaction has to be fast
 We have to know the stoichiometry of the
reaction
 The end point of the titration must be
identifiable and reproducible
Titration is complete when it meets the following
considerations:
 The equivalents of the titrant and the
analyte are the same (it reached the
equivalence point)
 The equivalence point is the point of
titration where the amount of titrant is
exactly that dictated by the stoichiometry
of the analyte
 The equivalence point is the ideal result in
titration. In effect, what is measured is the
end point of a sudden variation in the
physical or chemical property of a solution
CHEMICAL AND PHYSICAL CHANGES
ASSOCIATED WITH THE EQUIVALENCE
POINT OF TITRATION
 The analyte or the substance which is added
specially (called indicator) changes color
 There is clouding or turbidity in the solution
because of the formation of an insoluble
phase
 The electric conductivity of the solution
changes
 There is a change in the potential difference
between two electrodes immersed in a
solution
 The refraction index of the solution changes
 There is a temperature change
 There is a variation in the amount of current
passes through the solution
Standard Solution – solution of known
concentration, stable and no change in concentration.
The validity of an analytical procedure depends on
knowing how much reagent has been used. It is
possible to work out the exact how much
concentration of a titrant.
 Primary Standard
o A substance of high purity used for
standardization
o A sufficiently pure compound that can
be used to prepare a standard solution
by weighing out a certain amount and
then diluting it to a defined volume of
a solution in a volumetric flask
 Secondary Standard
o A substance whose concentration is
determined by reference to a primary
standard
Standardization – process of determining the
concentration of unknown solution
REQUIREMENTS FOR CHEMICALS TO BE
USED AS A PRIMARY STANDARD
 Purity
 Stability
 Undergo rapid reaction and stoichiometric
 High equivalence weight
 Absence of hydrate water
 Model cost
 Soluble
Note: The reaction is considered slow if its rate is less
than the normal state mixing of the sample and titrant

TITRATION TYPES
1. By reaction types
a. Precipitation method
- Detected by visual indicator method or by
a potentiometric titration
- A substance is titrated by precipitating it
with a saturated solution of an acid
b. Acid-base or neutralization method
- Small amount of indicator for organic
compound
- Acidimetry: acidic substance is titrated
with a substance with a standard solution
- Alkalimetry: basic substance titrated with a
standard solution of an acid
c. Complex formation or Complexiometric
- A substance is titrated with the reagent to
the formation complex
d. Redox or oxidation reduction method
- Use for elements that have more than one
oxidation
- A reducing substance is titrated with
saturated solution of an oxidizing agent or
vice versa
2. By indicator
- Spectrophotometric
- Electrochemical
- pH
METHODS USED
 Direct Method
o In which substance to be measured is
directly determined by titration to an
end point with a saturated solution
 Indirect Method
o In which substance itself is not
measured but by a quantity of reagent
is added to which is known to be
excess with respond to specific
reaction and the unused excess
undetermined by titration
VOLUMETRIC ANALYSIS REQUIREMENTS
 Accurate balance
 Graduated instruments
 Saturated solutions
 Indicators
Back titration
 Alternative technique to direct titration
 In a simple acid-base titration, a base (reagent)
is added in a known quantity – greater than
the amount required for acid neutralization
 Acid and base reacts completely
 The remaining base is titrated with a standard
acid
 The system has gone from being acid, past the
equivalence point to the basic (excess base),
and back to the equivalence point again. The
final titration to the equivalence point is called
BACK TITRATION.
PROPERTIES OF BACK TITRATION
 React with the excess volume of reactant
which has been left over after completing
reaction with the analyte from the normal
titration.
 The substance or solution of unknown
concentration of excess intermediate
reactant is made to react with known
volume and concentration of intermediate
reactant solution in back titration.
 Throughout back titration, the reaction
can reach the completion quickly as the
excess reactant that react with the NaOH
(as example) heated, and is much easier to
measure.
 Back titration also is an indirect titration
procedure.
 The proportion consumed in the reaction
of back titration being obtained is
difference.
PURPOSE OF BACK TITRATION
Back titration is designed to resolve some of the
problems encountered with forward or direct
titration. Possible reasons for devising back titration
technique are:
1. The analyte may be in solid form
2. The analyte may contain impurities which may
interfere with direct titration.
3. The analyte reacts slowly with titrant in direct
or forward titration. The reaction with the
intermediate reactant can be speeded up and
reaction can be completed say by heating.
4. Weak acid – weak base reactions can be
subjected to back titration for analysis of
solution of unknown concentration.
ADVANTAGES OF BACK TITRATION
 Useful if the end point of the reverse titration
is easier to identify than the end point of the
normal titration.
 Useful when trying to work out the amount of
an acid or base in a non-soluble solid.
DISADVANTAGES OF BACK TITRATION
 Needs skill and practice for effective results
 Instruments have to be properly calibrated
since it will affect final results
  Reactivity of the elements to be titrated
should be well researched since this may
affect the end point
 Time consuming if done manually
 Indicators property must be known
PROCEDURE FOR TITRATION
1. Obtain the items listed in the “Things you’ll
need” section
2. Rinse and purge your burette
3. Clean and rinse all glassware with tap water
using some detergent if necessary. Be very
careful with burettes as they are very fragile.
Always hold them with two hands.
4. Rinse all glassware with distilled water to
lower the chances of contamination
5. Measure out a precise amount of analyte
6. Fill your beaker or Erlenmeyer flask with a
small amount of distilled water.
7. Rinse the analyte into your beaker or
Erlenmeyer flask, thus making sure all of the
analyte is in the beaker.
8. Put a small amount (4-5 drops) of the
appropriate color indicator into the beaker.
9. Agitate the beaker’s contents by swirling the
beaker.
10. Fill the burette with an excess amount of
titrant. The titrant should be in an aqueous
form.
11. Clamp the burette carefully to a burette stand.
The tip of the burette should not be touching
any surfaces.
12. Place the beaker under the burette.
13. Hit the stood burette carefully with your index
finger in order to remove the bulb gases inside
the liquid then record the initial volume of the
burette at the meniscus (the lowest part of the
dip in the liquid)
14. Turn the stopcock of the burette vertical, so
that the titrant is added to the beaker. Only let
a small amount of the titrant out. A color
change should occur. Agitate the beaker until
the color disappears.
15. Repeat the above step until the color persists
slightly.
16. Record the volume of the burette.
17. Add titrant drop by drop as you near the
endpoint.
18. Agitate the beaker’s contents after every drop.
19. Stop when you’ve reached endpoint, which is
the point when the reactant within the analyte
has been completely neutralized. You can tell
you’ve reached the endpoint with a color
change, depending on which indicator you
choose to use.
20. Record your final volume.
21. Add drops of titrant until you pass endpoint.
At this point, the beaker’s contents should be
entirely the color of the color indicator when
titrant is added.
22. Clean up by wiping away all standing water.
23. Dispose of the chemicals used in a labeled
waste container.
24. Calculate the concentration of the reactant
within the analyte using the data gathered.
APPLICATION OF QUALITATIVE
ANALYSIS IN OIL AND GAS INDUSTRY
Hydrocarbons
 Dry gas (methane)
 Wet gases (ethane, propane, butane)
Condensates – hydrocarbons that are gaseous in the
subsurface but condense to liquid when they are
cooled at the surface.
Liquid hydrocarbons – oil, crude oil or crude
Plastic hydrocarbons – includes asphalt and related
substances
Solid hydrocarbons – include coal and kerogen
Gas hydrates – are ice crystals with peculiarly
structured atomic lattices, which contain molecules of
methane and other gases.
Natural gas – mixture of hydrocarbons and varying
quantities of nonhydrocarbons that exists either in the
gaseous phase or in solution with crude oil in natural
background reservoirs.
Dissolved gas – solution in crude oil in the contact
with crude oil in the reservoir.
Nonassociated gas – is in reservoirs that do not
contain significant quantities of crude oil.
Natural gas liquids (NGLs) – portions of the
reservoir gas that are liquefied at the surface in lease
operations, field facilities or gas processing plants.
 Ethane
 Propane
 Butane
 Pentane
 Natural gasoline
 Condensate
2 groups of natural gases that are encountered in
the subsurface:
1. Organic origin
2. Inorganic origin
Gases:
1. Dry gas – with less than 0.1 gal/1000 ft3 of
condensate; largely methane.
2. Wet gas – with more than 0.3 gal/1000 ft3 of
condensate; contains ethane, butane and propane.
Note: gases can also be described as sweet or sour
based on the absence or presence of hydrogen sulfide.
PHYSICAL AND CHEMICAL PROPERTIES
OF CRUDE OIL AND OIL PRODUCTS
Density
- mass per unit volume of a fluid.
- State function and for a pure compound
depends on both temperature and pressure
Liquid densities decrease as temperature increases
but the effect of pressure on liquid densities at
moderate pressures is usually negligible.
Viscosity
- (of oil) is a measure of its resistance to internal
flow and an indication of its oiliness in the
lubrication of surfaces.
- Two types: Dynamic and Kinematics viscosity
Pour point
- Lowest temperature at which the sample will
flow and is a rough indicator of the relative
paraffinicity and aromaticity of the crude.
- A lower pour point means that the paraffin
contents is low and greater content of
aromatics.
Carbon residue
- Determined by distillation to a coke residue in
the absence of air.
- The lower the carbon reside, the more
valuable the crude.
Salt content, lb/1000 bbl
- If the salt content of the crude, when
expressed as NaCl, is greater than 10 lb/1000
bbl, it is generally necessary to desalt the crude
before processing. If the salt is not removed,
severe corrosion problems may be
encountered.
Sulfur content
- (and APA gravity) have the greatest influence
on the value of crude oil although nitrogen
and metals contents are increasing in
importance.
Flash point
- Minimum temperature at which vapor
pressure of the hydrocarbon is sufficient to
produce the vapor needed for spontaneous
ignition of the hydrocarbon with the air with
the presence of an external source.
Gas/oil ratio
- Ratio of components that exist in the gas
phase at surface conditions to the rest of the
petroleum.
Wax content
- Reflection of the amount of high molecular
weight saturated compounds.
HYDROCARBON GASES
 Biogenic gases – formed in organic-rich
sediments using diagenesis by a specialized
group of bacteria “methanogens”
o Methanogenic bacteria – require
anoxic, sulphate-free environments at
temperatures below approximately 75
degree C.
 Thermogenic gases
o Oil associated gases – form from
kerogen at the same time as oil is
generated. Short chain component of
the oil and are believed to be derived
from lipids of organisms.
o Non-associated gases – derived from
lignin, a component of higher land
plants. They are the dominant
component of gases derived from
coals.
NON-HYDROCARBON GASES
 Nitrogen – can be derived from basement
rock, particularly from igneous sources. It is
generated from organic matter, particularly
during the advanced stages of maturation.
 Carbon dioxide – has a number of possible
sources although most of these usually only
contribute small quantities of gas.
 Hydrogen Sulphide – unpleasant, toxic gas
occasionally found in large quantities in
reservoirs. Three main sources:
o Bacterial sulphate reduction
o Thermal cracking of kerogen or oil
o Gas souring
The major source of H2S is via thermal cracking of
kerogen or oil.
INSTRUMENTS UDES IN DETERMINING
PETROLEUM PROPERTIES
Asphaltene separation and liquid
chromatography
Gas chromatography